Method of cementing using polymeric retarder

ABSTRACT

Set retarders of copolymers of at least one polymerizable ethylenically unsaturated monomer and at least one alkoxylated monomer are capable of delaying the hardening of a cementitious slurry when introduced into a subterranean formation until a downhole temperature greater than or equal to 500° F. is obtained, even in the absence of an intensifier.

This application is a continuation-in-part application of U.S. patent application Ser. No. 11/601,512, filed on Nov. 17, 2007.

FIELD OF THE INVENTION

The invention relates to methods of cementing an oil, gas or geothermal well at elevated temperatures using an alkoxylated copolymer as retardant and dispersant.

BACKGROUND OF THE INVENTION

Hydraulic cements are cements that set and develop compressive strength due to a hydration reaction, and thus can be set under water. As such, hydraulic cements are often used for cementing pipes or casings within a wellbore of a subterranean formation as well as other purposes, such as squeeze cementing. In the drilling industry, successful cementing of well pipe and casing during oil, gas, and geothermal well completion requires cement slurries having several important properties. The cement slurry must have a pumpable viscosity, fluid loss control, minimized settling of particles and the ability to set within a practical time.

In a typical completion operation, the cement slurry is pumped down the inside of the pipe or casing and back up the outside of the pipe or casing through the annular space. This seals the subterranean zones in the formation and supports the casing. Under normal conditions, hydraulic cements, such as Portland cement, quickly develop compressive strength upon introduction to a subterranean formation, typically within 48 hours from introduction. As time progresses, the cement develops greater strength while hydration continues.

It is common to use a set retarder with the hydraulic cement in order to delay the set time of the cement composition. Such set retarders are particularly useful when the cement composition is exposed to high subterranean temperatures. In addition to being capable of delaying the set time of the cement composition, the set retarder also functions to extend the time the cement composition remains pumpable after the cement composition is mixed and before it is placed into the desired location.

In use, many of the set retarders of the prior art exhibit unpredictable retardation of the set time of the cement composition especially at elevated temperatures. For instance, lignosulphonates or gluconates are often used with borate retarder intensifiers to retard Portland cement in oil wells at temperatures in excess of 350° F. Such set retarder compositions, however, are only somewhat effective as downhole temperatures increase to 500° F.

A need therefore exists for the development of cement compositions containing a set retarder (preferably which does not require an intensifier) and which is effective at downhole temperatures in excess of 500° F.

SUMMARY OF THE INVENTION

Copolymers of at least one polymerizable ethylenically unsaturated monomer and at least one alkoxylated monomer may be employed to retard the set time of a cementitious slurry introduced into a subterranean formation penetrated by a wellbore. The set retarder is capable of delaying the hardening of the cementitious slurry until a downhole temperature greater than or equal to 500° F. is obtained, even in the absence of an intensifier.

In an embodiment, the set retarder may contain at least one alkoxylated monomer which may exist in the form of a sulfate, phosphate or ketonic salt.

Suitable set retarders include those of the formula:

wherein unit E represents the polymerizable ethylenically unsaturated monomer, the second monomer represents an alkoxylated sulfate, phosphate or ketonic salt and F represents an alkoxylated monomer which may be used in combination with or in place of the second monomer.

In a preferred embodiment, the set retarder is a copolymer of formula (I) above wherein:

R1 is H or a C₁-C₄ alkyl;

G is —CH₂ or —CHCH₃;

R2 is —(CH₂CH₂—O—)_(n), —(CH₂CH(CH₃)—O—)_(n) or —(CH(CH₃)CH₂—O—)_(n) or a mixture thereof;

n ranges from about 1 to about 100;

X is an anionic radical selected from —SO₃ ⁻, —PO₃ ²⁻, —COO⁻ or —CH₂—;

Z is —H or a water soluble cationic moiety which counterbalances the valence of the anionic radical X;

c is a positive integer; and

d and e are 0 or positive integers provided that d and e are not both 0.

In a preferred embodiment, E is a carboxylic acid, amido carboxylic acid, carboxylic acid ester (such as a C₁-C₆ alkyl ester of carboxylic acid), amido carboxylic acid ester (such as a C₁-C₆ alkyl ester of amido carboxylic acid), hydroxylated alkyl ester of a carboxylic acid (such as a hydroxylated C₁-C₆ alkyl ester of carboxylic acid) or a hydroxylated amido carboxylic acid ester (such as a C₁-C₆ hydroxylated amido carboxylic acid ester), sulfonic acid, phosphonic acid or amide as well as mixtures thereof.

In another preferred embodiment, the second monomer of formula (I) is an alkoxylated alcohol sulfate, such as of the formula:

wherein R2 and Z have the meanings set forth above.

The third monomer, F, of formula (I) is preferably of the structure:

wherein:

R4 is H or a straight or branched chain C₁-C₄ alkyl;

R5 is a hydroxy substituted alkyl or alkylene having from 1 to 6 carbon atoms, —(CH₂CH₂—O—)_(n), —(CH₂CH(CH₃)—O—)_(n), —(CH(CH₃)CH₂—O—)_(n) or a mixture thereof;

R6 is —CH₂ or —C═O;

R7 is —H or a C₁-C₁₈ straight or branched alkyl chain, preferably a lower (C₁-C₄) alkyl, or an acetate formed as a cap on the polyethyleneglycol allyl ether by reacting an acetylating agent with an allyl ether of polyethyleneglycol to produce an acetate capped polyethyleneglycol allyl ether; or XZ (XZ having been defined as above); and

n is an integer from about 1 to about 150, preferably from 1 to about 40.

In a preferred embodiment, the set retarder is a water soluble copolymer of the structure:

The weight average molecular weight of the copolymer is between from about 1,000 to about 1,000,000 Daltons, preferably from about 1,500 to about 50,000 Daltons, most preferably about 25,000 Daltons.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The set retarder used in the invention is a water-soluble or water-dispersible copolymer containing at least one polymerizable ethylenically unsaturated monomer and at least one alkoxyated monomer. The set retarder is used with an aqueous slurry of cement for introduction into a gas, oil or geothermal well.

The set retarder is capable of delaying the set time of the cementitious composition until the slurry is placed into its desired location. When used, the set time of the aqueous slurry may be delayed until downhole temperatures as high as 500° F., even as high as 600° F., are obtained. Thus, the aqueous slurry may be hardened to a solid mass at elevated temperatures within the wellbore. Further, the aqueous slurries used in the invention may exhibit set times at elevated temperatures even in the absence of an intensifier.

In its preferred embodiments, the copolymer used in the cementitious slurry may contain the units:

wherein the first monomer, E, depicted in (V) represents the polymerizable ethylenically unsaturated monomer. The sulfate, phosphate or ketonic salt is the second depicted monomer (“F”) in formula (V) and the third monomer (“G”) of formula (V) is an alkoxylated monomer which may include an acetate. (As used herein, the term “copolymer” includes a polymer derived from two or more monomers. As such, the term “copolymer” includes “terpolymers”.)

In a preferred embodiment, c is a positive integer and unit E is a carboxylic acid, amido carboxylic acid, carboxylic acid ester (such as a C₁-C₆ alkyl ester of carboxylic acid), amido carboxylic acid ester (such as a C₁-C₆ alkyl ester of amido carboxylic acid), hydroxylated alkyl ester of a carboxylic acid (such as a hydroxylated C₁-C₆ alkyl ester of carboxylic acid) or a hydroxylated amido carboxylic acid ester (such as a C₁-C₆ hydroxylated amido carboxylic acid ester), sulfonic acid, phosphonic acid or amide as well as mixtures thereof.

More preferably, unit E is at least one member selected from acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methyl acrylamide, N,N-dimethyl acrylamide, N-isopropylacrylamide, maleic acid or anhydride, fumaric acid, itaconic acid, styrene sulfonic acid, vinyl sulfonic acid, isopropenyl phosphonic acid, vinyl phosphonic acid, vinylidene di-phosphonic acid, 2-acrylamido-2-methylpropane sulfonic acid and mixtures thereof and especially acrylic acid, methacrylic acid, acrylamide, maleic acid, maleic anhydride, fumaric acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid and water-soluble salts thereof. In a most preferred embodiment, the polymerizable ethylenically unsaturated monomer is acrylic acid or methacrylic acid. In another preferred embodiment, the polymerizable ethylenically unsaturated monomer constitutes a mixture of acrylic acid and 2-acrylamido-2-methylpropane sulfonic acid. Water-soluble salts of such acids may also be used.

In a preferred embodiment, the molar ratio of E to F to G in the copolymer is in a range of from about 1 to about 10 for E, from 0 to about 4 for F, and from 0 to about 10 for G. In an embodiment, the molar ratio c:d ranges in formula (V) may range from about 30:1 to about 1:20. Preferably, the molar ratio of c:d ranges from about 15:1 to 1:10. More preferably, the molar ratio of E to F to G in the copolymerization product is in a range of from about 2.5 to about 6 for E, from about 0 to about 2 for F, and from about 1 to about 3 for G.

In the second (F) monomer of formula (V), R1 is H or a C₁-C₄ alkyl, preferably —H; G is —CH₂— or —CHCH₃—; R2 is —(CH₂CH₂—O—)_(n), —(CH₂CH(CH₃)—O—)_(n), —(CH(CH₃)CH₂—O—)_(n) or a mixture thereof, wherein n ranges from about 1 to about 100, preferably from about 1 to about 20; X is an anionic radical selected from —SO₃ ⁻, —PO₃ ²⁻ or —COO⁻; preferably —SO₃ ⁻; Z is H or a water soluble cationic moiety which counterbalances the valence of the anionic radical X, including but not limited to Na⁺, K⁺, Ca²⁺ or NH₄ ⁺, or an organic amine such as triethylamine or morpholine, c and d are positive integers.

In a preferred embodiment, the copolymer is of formula (V) wherein F is an alkoxylated alcohol sulfate, such as of the formula:

The monomer F can be prepared by ethoxylation, propoxylation or a combination of the ethoxylation and propoxylation of an allyl alcohol followed by an addition of sulfamic acid. The resultant is a monomer unit having a covalently bonded sulfate terminated end group bonded through an oxygen atom. A preferred copolymer, where e is 0, is acrylic acid/polyethyleneglycol monoallyl ether sulfate (APEGS) of the formula:

wherein n ranges from about 1 to about 100, preferably from about 1 to about 20; Z is hydrogen or a water-soluble cation such as Na, K, Ca or NH₄.

R4 of monomer G of formula (V) is —H or a straight or branched chain C₁-C₄ alkyl; R5 is a hydroxy substituted alkyl or alkylene having from 1 to 6 carbon atoms, —(CH₂CH₂—O—)_(n), —(CH₂CH(CH₃)—O—)_(n), —(CH(CH₃)CH₂—O—)_(n) or a mixture thereof; R6 is —CH₂ or —C═O; R7 is —H or a C₁-C₁₈ straight or branched alkyl chain, preferably a lower (C₁-C₄) alkyl, or an acetate formed as a cap on the polyethyleneglycol allyl ether by reacting an acetylating agent with an allyl ether of polyethyleneglycol to produce an acetate capped polyethyleneglycol allyl ether; or XZ (XZ having been defined as above); and n is an integer from about 1 to about 150, preferably from about 1 to about 40. Suitable acetylating agents include acetic acid, acetic anhydride, acetyl chloride, and the like as described in U.S. Pat. Nos. 4,959,156 and 4,847,410, incorporated herein by reference.

In an embodiment, d is 0 and the copolymer contains repeating units of E and G. A preferred copolymer of formula (V) where d is 0 is an acrylic acid, methacrylic acid or maleic acid/polyalkyleneglycol allyl ether copolymer of the general formula:

wherein R4 is H or lower C₁-C₄ alkyl, R5 is —(CH₂CH₂—O—)_(n) or —(CH₂CH(CH₃)—O—)_(n) or —(CH(CH₃)CH₂—O—)_(n) or a mixture of thereof, n is an integer of from 1 to about 40, R7 is H, lower C₁-C₄ alkyl or an acetate, R9 is —H or —COOM, R10 is H or C₁-C₄ alkyl, R11 is COOM and M is H or a water soluble cation, c is the molar percentage being between 1-99 molar % (preferably 30-70 molar %), e is the molar percentage being between 99-1 molar % (preferably 70-30 molar %), and c and e should add up to 100%. Acrylic acid (R11=H, R10=H) or methacrylic acid (R9=H, R10=CH₃) may be replaced with maleic acid (R9=COOH, R10=H).

The number average molecular weight of the water soluble or water dispersible copolymers of Formula (VII) may fall within the Mn range of about 1,000 to 100,000 desirably, 1,000 to 30,000 and more desirably 1,500 to 10,000.

Preferred as monomer G of formula (V) are (a) polyethylene glycol allyl ether (PEGAE) wherein R4 and R7 are both H, R6 is CH₂ and R5 is —(CH₂CH₂—O—)_(n); (b) polypropylene glycol allyl ether (PPGAE) wherein R4 and R7 are both H, R6 is CH₂ and R5 is —(CH₂CH(CH₃)—O—)_(n) or —(CH(CH₃)CH₂—O—)_(n) or a mixture of both; (c) polyethylene glycol/propylene glycol allyl ether (PEGPGAE) wherein R4 and R7 are both H, R6 is —CH₂— and R5 is —(CH₂CH₂—O—CH₂CH(CH₃)—O—)_(n) or —(CH₂CH₂—O—CH(CH₃)CH₂—O—)_(n); (d) hydroxyethyleneglycolmethyl methacrylate (HEME) wherein R4 is CH₃, R6 is —C═O, R5 is —(CH₂CH₂—O—) and R7 is —H; and (e) methoxyethyleneglycolmethyl methacrylate (MHEM) wherein R4 is —CH₃, R6 is —C═O, R5 is —(CH₂CH₂—O—); and R7 is —CH₃. In each of these preferred monomers, R7 may be sulfonated.

Preferred as monomer G of formula (V), that is where e is a positive integer, is acrylic acid/polyethyleneglycol monoallyl ether sulfate/1-allyloxy-2-hydroxypropyl-3-sulfonic acid of the structure of Formula V:

wherein n ranges from about 1 to about 100, preferably from about 1 to about 20; Z is hydrogen or a water-soluble cation (such as Na, K, Ca or NH₄) and wherein Z may be the same or different in c, d and e. The molar ratio of c:d in formula (III) is between from about 30:1 to about 1:20 and the molar ratio of c:d:e in formula (IV) is between from about 20:10:1 to about 1:1:20.

The copolymer may be produced by solution, emulsion, micelle or dispersion polymerization techniques. Conventional polymerization initiators such as persulfates, peroxides, and azo type initiators may be used. Polymerization may also be initiated by radiation or ultraviolet mechanisms. Chain transfer agents such as isopropanol, allyl alcohol, hypophosphites, amines or mercapto compounds may be used to regulate the molecular weight of the polymer. Branching agents, such as methylene bisacrylamide and polyethylene glycol diacrylate and other multifunctional crosslinking agents, may further be added. The resulting polymer may be isolated by precipitation or other well-known techniques. If polymerization is in an aqueous solution, the polymer may simply be used in the aqueous solution form.

A preferred terpolymer of the present invention, that is where e is a positive The weight average molecular weight of the copolymer is between from about 1,000 to about 1,000,000 Daltons, preferably from about 1,500 to about 50,000 Daltons, most preferably about 25,000 Daltons.

In a most preferred embodiment, the copolymer may be selected from one or more of the copolymers set forth in Table I below:

TABLE I monomer mole % Viscosity, Copolymer ratio solids cP pH aa:apes-10  3:1 1 24.3 31.7 5.4 ″ 3:1 24.1 21.8 5.8 aa:apes-20 2.5:1  25.2 12.3 5.5 ″ 3:1 23.7 18.7 5.2 ″ 4:1 23.6 21 5.1 ″ 5.6:1  25.6 65.9 5.9 ″ 8.9:1  23.1 8850 6.4 aa:apes-50 3:1 24.6 19.3 4.7 3:1 24.6 14.8 4.6 aa:ape5-p5s 3:1 24.2 13 5.5 3:1 24.8 11 6.0 maa/apae5-p5s 3:1 25.2 10.6 6.4 maa/aa/apes-10 1.5:1.5:1 24 31.2 6.1 aa/apes-10/pegae-10 3:0.5:0.5 23.8 31.5 5.4 aa/apes-20/pegae-20 3:0.5:0.5 25.1 20.3 5.5 aa/apes-50/pegae-50 3:0.5:0.5 24.5 16.5 4.9 aa/apes-20/pegae-50 3:0.5:0.5 25 14 5.1 aa/apes-20/pegae-20 3:0.27:0.5 23.7 19 6.0 aa/apes-20/pegae-20 3:0.27:0.5 25.7 50.5 6.1 aa/apes-20/pegae-60 3:0.5:0.5 24.9 18.3 5.2 aa/apes-20/pegae5-p5 3:0.5:0.5 24.8 14.2 5.5 aa/apae5-p5s/pegae-50 3:0.5:0.5 24.7 17.1 5.2 aa/apes-20/pegae-100 3:0.5:0.5 40.2 86.3 6.0 aa/mhem-16/apes-20 3:0.5:0.5 24.4 19.7 6.6 aa/apes-20/pegae5-p5 3:0.5:0.5 24.3 14.1 5.8 aa/apes-20/pegae5-p5 3:0.5:0.5 24.84 14.2 5.5 wherein aa is acrylic acid, maa is methyl(meth)acrylate; apes-10 is ammonium allylpolyethoxy (10) sulfate (alkoxylated with an average of 10 moles of ethylene oxide), apes-20 is ammonium allylpolyethoxy (20) sulfate (alkoxylated with an average of 20 moles of ethylene oxide), apes-50 is ammonium allylpolyethoxy (50) sulfate (alkoxylated with an average of 50 moles of ethylene oxide), ape5-p5s is ammonium allylpolyethoxy (5) polypropoxy (5) sulfate ((alkoxylated with an average of 5 moles of ethylene oxide and 10 moles of propylene oxide), pegae-10 is polyethylene glycol (10) allyl ether (alkoxylated with an average of 10 moles of ethylene oxide); pegae-20 is polyethylene glycol (20) allyl ether (alkoxylated with an average of 20 moles of ethylene oxide), pegae-50 is polyethylene glycol (50) allyl ether (alkoxylated with an average of 50 moles of ethylene oxide), pegae-60 is polyethylene glycol (60) allyl ether (alkoxylated with an average of 60 moles of ethylene oxide), pegae-100 is polyethylene glycol (100) allyl ether (alkoxylated with an average of 100 moles of ethylene oxide); and MHEM16 is methoxypolyethylene glycol monomethacrylate (alkoxylated with an average of 16 moles of ethylene oxide).

The weight average molecular weight of the copolymer is between from about 1,000 to about 1,000,000 Daltons, preferably from about 1,500 to about 50,000.

Hydraulically-active cementitious materials, suitable for use in the cementitious slurry, include materials with hydraulic properties, such as hydraulic cement, slag and blends of hydraulic cement and slag (slagment), which are well known in the art. The term “hydraulic cement” refers to any inorganic cement that hardens or sets due to hydration. As used herein, the term “hydraulically-active” refers to properties of a cementitious material that allow the material to set in a manner like hydraulic cement, either with or without additional activation. Hydraulically-active cementitious materials may also have minor amounts of extenders such as bentonite, gilsonite, and cementitious materials used either without any appreciable sand or aggregate material or admixed with a granular filling material such as sand, ground limestone, the like. Strength enhancers such as silica powder or silica flour can be employed as well. Hydraulic cements, for instance, include Portland cements, aluminous cements, pozzolan cements, fly ash cements, and the like. Thus, for example, any of the oilwell type cements of the class “A-H” as listed in the API Spec 10, (1st ed., 1982), are suitable hydraulic cements. In addition, the cementitious material may include silica sand/flour and/or weighing agents including hematite or barite.

Mixing water is utilized with the dry cement composition to produce a fluid pumpable slurry of suitable consistency. API Spec 10, Second Edition, June 1984 which is known in the cement industry, describes an approved apparatus and method for measuring the consistency of cement slurries in terms of Bearden units of consistency (Bc). A pumpable slurry should measure in the range from about 1 to about 30 Bc and preferably be greater than 5 Bc. Slurries thinner than about 5 Bc will tend to have greater particle settling and free water generation.

Depending upon the particular slurry and intended conditions of use, mixing water is utilized in the slurry of the present invention in the range from about 30 to 150 weight percent based upon the dry weight of cement and preferably is in the range of about 35 to 90 weight percent.

The cementitious slurry of the invention may further contain conventional additives used in the cementing of a gas, oil or geothermal wellbore such as suspending or thixotropic agents, fluid loss control additives, strength retrogression additives, permeability reducers, weighting materials, permeability reducers and anti-settling agents, etc.

The set retarders employed in the cementitious slurries of the invention do not require an intensifier. In fact, the cementitious slurries typically exhibit retardation of set time at temperatures in excess of 600° F. If desired, intensifiers known in the art, such as those disclosed in U.S. Pat. No. 5,105,885, may be employed.

The following examples are illustrative of some of the embodiments of the present invention. Other embodiments within the scope of the claims herein will be apparent to one skilled in the art from consideration of the description set forth herein. It is intended that the specification, together with the examples, be considered exemplary only, with the scope and spirit of the invention being indicated by the claims which follow.

All percentages set forth in the Examples are given in terms of weight units except as may otherwise be indicated.

EXAMPLES

In each of the Examples, a hydraulic cement, water, set retarder and remaining additives were mixed together to form a pumpable slurry. The cement slurry was then pumped to the desired location in the wellbore and allowed to harden to form a solid mass. The abbreviations used in the tables have the following meanings:

PPG, pounds per gallon

GPS, gallons per sack

W-10, a weighting material having a particle size of 5 microns, a product of BJ Services Company;

100 mesh refers to 100 mesh silica sand (versus approximately 325 mesh for silica flour), strength retrogression additives;

BA-11, a bonding agent and permeability reducer, a product of BJ Services Company;

BA-90, uncompacted silica fume, a permeability reducer and a product of BJ Services Company;

FLR-1, a high molecular weight polyacrylate fluid loss additive, a product of Fritz Industries;

FL-63, a high molecular weight grafted tannin, a product of Aqualon, a division of Hercules, Inc.

ASA-500, a polymeric dry blend used as an anti-settling agent to eliminate free fluid development in cement slurries, a product of BJ Services Company;

ASA-301, an anti-settling agent of BJ Services Company;

SMS refers to sodium metasilicate, an anti-settling agent;

Coag-139 and APO600 refer to acrylic acid/polyethylene glycol allyl ether copolymers, commercially available from GE Betz Company;

DCA-229L refers to an acrylic acid/ammonium allylpolyethoxy (10) sulfate copolymer, a product of GE Betz Company.

MPA-3 refers to wollastonite.

APO100 refers to diluted Coag-139, in approximately 15 weight percent water;

Cementitious slurries were prepared by mixing neat Class H Portland cement and fresh water at 16.4, 17.5 and 18 pounds per gallon (ppg). To the slurry was added an amount in gallons per sack of cement (gps) of set retarder along with other designated additives at room temperature. The resultant slurries were kept with occasional agitation.

Standard API viscosity and fluid loss tests were conducted on the cement slurries; the viscosity being measured against industry standard torque measurement of 70/100 Bc (representing the amount of torque required to move the paddle through the cement slurry). Set retardation continued for about 6 hours. The results and amount of additives (percentages are by weight of cement, BWOC) are set forth in Tables II-VIII below. Temperatures are at ° F. The “Thickening Time” represents the amount of time (hrs:minutes) that the slurry remained in a liquid state, for instance the measurement “5:45/5:46” refers to the amount of time for the cement slurry to reach 70/100 Bc and thus is indicative of the amount of time that the cement slurry remains pumpable at the stated temperature. Illustrative for the data for compressive strength, as set forth in Example 7, of “500/17:40” refers to the fact that the cement slurry exhibited a compressive strength of 500 psi after 17 hours and 40 minutes.

TABLE II Compressive Silica 100 Thickening Strength Ex. W-10 Flour mesh BA-90 BA-11 FLR-1 ASA-500 Coag-139 Temp. Time Fluid psi/time No. Density % % % % % % % gps ° F. 70/100 Bc Loss (hrs:min) 1 17.5  10 35 4 1 1   0.3 0.2 312 5:45/5:46 2 18   25 35 4 1 1   0.3 0.2 345 1:36/1:38 3 ″ ″ ″ 3 ″ ″ ″ ″ ″ 1:26/1:28 4 ″ ″ ″ 4 ″ ″ ″ 0.225 ″ 2:10/2:11 5 ″ ″ ″ ″ ″ ″ ″ 0.25 ″ 3:36/3:37 6 ″ ″ ″ ″ ″ ″ ″ 0.275 ″ 5:45/5:47 18 500/17:40: 1737/24: 2290/48 7 8 ″ ″ ″ ″ ″ ″ ″ 0.28 ″ 8:35/8:36 9 16.4  35 2   1.5   0.75   0.3 0.2 370 10 16.4  ″ ″ ″ 1 ″ ″ ″ 6:53/6:54 28 500/16:26: 3776/24 11 ″ ″ 3 ″ ″ ″ ″ ″ 5:06/5:07 12 ″ ″ 4 ″ ″ ″ ″ ″ 3:03/3:09 13 ″ ″ ″ ″ ″ ″ 0.225 ″ 4:26/4:27 14 ″ ″ ″ ″ ″ ″ 0.23 ″ 5:50/5:51 15 ″ ″ ″ ″ ″ ″ 0.25 ″ 10:32/10:33 16 16.48 35 1 0.1 200 31:30:00 17 16.48 35 1 0.1 300 1:56 18 ″ ″ ″ 0.15 ″ 3:07 19 ″ ″ ″ 0.175 ″ 45:11:00 20 16.48 35 1 0.1 400 1:17 21 ″ ″ ″ 0.15 ″ 1:36 22 ″ ″ ″ 0.175 ″ 6:33 23 ″ ″ ″ 0.2 ″ 10:40  24 16.48 35 1 0.2 500 3:16 25 ″ ″ 0.225 ″ 7:51 26 ″ ″ ″ 0.25 ″ 8:50 27 ″ ″ ″ 0.3 ″ 10:24  28 16.48 35 1 0.4 600 3:10 29 ″ ″ ″ 0.5 ″ 3:22 30 ″ ″ ″ 0.7 ″ 3:42

TABLE III Thickening Silica Time Ex. Density Flour ASA-301 ASA-500 SMS APO100 Temp. hrs:min No. ppg % % % % gps ° F. 70/100 Bc 31 16.5 35 0.2 0.05 201 3:34/3:38 32 ″ ″ ″ 0.1 ″ 15:49/15:53 33 ″ ″ 0.05 ″ 3:50/3:53 34 ″ ″ 0.1 ″ 8:35/8:38 35 ″ ″ 0.2 0.1 ″ 3:00/3:04 36 ″ ″ ″ 0.2 ″ 37 16.5 35 0.2 0.1 258 1:48/1:49 38 ″ ″ ″ 0.2 ″ 3:06/3:08 39 ″ ″ ″ 0.3 ″ 5:10/5:11 40 16.5 35 0.2 0.2 291 1:55/1:56 41 ″ ″ ″ 0.25 ″ 2:47/2:48 42 ″ ″ ″ 0.3 ″ 4:40/4:40 43 ″ ″ ″ 0.35 ″ 6:17/6:18 44 ″ ″ ″ 0.4 ″ 23:13/23:14 45 16.5 35 0.2 0.3 364 1:41/1:42 46 ″ ″ ″ 0.35 ″ 8:24/8:25 47 ″ ″ ″ 0.4 ″ 24:18/24:18 48 ″ ″ 0.5 0.2 ″ 1:17/1:18 49 ″ ″ ″ 0.25 ″ 2:15/2:15 50 ″ ″ ″ 0.3 ″ 18:47/18:48 51 ″ ″ ″ 0.35 ″ 29:51/29:52 52 16.5 35 0.5 0.25 404 1:10/1:10 53 ″ ″ ″ 0.275 ″ 2:49/2:50 54 ″ ″ ″ 0.3 ″ 7:01/7:02 55 ″ ″ ″ 0.35 ″ 20:34/20:34 56 ″ ″ ″ 0.4 ″ 23:46/23:47 57 16.5 35 0.5 0.3 444 3:04/3:04 58 ″ ″ 0.35 ″ 6:37/6:37 59 ″ ″ ″ 0.4 ″ 8:52/8:52 60 ″ ″ 0.5 ″ 11:55/11:55 61 16.5 35 0.5 0.4 484 4:29/4:30 62 ″ ″ 0.5 ″ 10:27/10:27

TABLE IV Thickening Silica Time Ex. Density Flour BA-90 ASA-500 BA-11 FL-63 APO 100 Temp. hrs:min No. Ppg % % % % % gps ° F. 70/100 63 16.2 35 3 1 0.8 0.22 250 3:39/3:41 64 ″ ″ ″ ″ ″ 0.24 ″ 3:52/3:54 65 ″ ″ ″ ″ ″ 0.26 ″ 4:16/4:18 66 16.2 35 3 1 0.8 0.2 275 2:07/2:09 67 ″ ″ ″ ″ ″ 0.22 ″ 2:15/2:17 68 ″ ″ ″ ″ ″ 0.24 ″ 2:24/2:25 69 ″ ″ ″ ″ ″ 0.28 ″ 2:39/2:40 70 ″ ″ ″ ″ ″ 0.32 ″ 3:06/3:07 71 ″ ″ ″ ″ ″ 0.35 ″ 4:50/4:53 72 ″ ″ ″ ″ ″ 0.38 ″ 15:53/15:55 73 16.5 35 1 1 1   0.25 360 1:38/1:39 74 ″ ″ ″ ″ ″ 0.3 ″ 2:03/2:04 75 ″ ″ ″ ″ ″ 0.325 ″   8:01/8:01? 76 ″ ″ ″ ″ ″ 0.35 ″ 13:07/13:07 77 ″ ″ ″ ″ 0.325 ″ 2:49/2:50 78 ″ ″ 1 ″ ″ ″ 1:35/1:36 79 ″ ″ 1 ″ 1.2 0.34 397 2:56/2:56 80 ″ ″ ″ ″ ″ 0.36 ″ 5:50/5:51 81 ″ ″ ″ ″ ″ 0.38 ″ 9:02/9:02 82 ″ ″ ″ ″ ″ 0.4 ″   8:39/8:40? 83 ″ ″ ″ ″ ″ 0.42 ″ 12:00+

TABLE V 100 Thickening Ex. Density Mesh MPA-3 ASA-500 BA-11 FL-63 APO 100 Temp. Time No. ppg % % % % % gps ° F. hrs:min 84 17.5 35 25 1 1 1 0.35 360 1:30/1:33 85 ″ ″ ″   0.5 ″ ″ 0.4 ″ 1:42/1:43 86 ″ ″ ″   0.25 ″ ″ 0.43 ″ 5:25/5:26 87 ″ ″ ″ ″ ″ ″ 0.45 ″ 5:53/5:53 88 ″ ″ ″ ″ ″ ″ 0.47 ″ 8:15/8:16 89 16.5 35 1 1 1 0.32 360 1:56/1:56 90 ″ ″ ″ ″ ″ 0.33 ″ 1:51/1:53 91 ″ ″ ″ ″ ″ 0.34 ″ 9:25/9:25 92 ″ ″ ″ ″ ″ 0.35 ″ 12:10/12:11 93 ″ ″ 25 ″ ″ ″ 0.34 ″ 94 16.5 35 1 1   1.2 0.34 397 1:32/1:41 95 ″ ″ ″ ″ ″ ″ ″ 1:40/1:47

TABLE VI Thickening 100 Time Ex. Density Mesh Hematite BA-58 FLR-1 APO 100 Temp. hrs:min No. ppg % % % % gps ° F. 70/100 96 18.5 35 30 5 1 422 97 ″ ″   27.5   7.5 ″ ″ 1:31/1:31 98 ″ ″ 25 10  ″ ″ 0:51/0:52 99 ″ ″ ″ ″ ″ ″ 0:52/0:53 100 ″ ″ ″ ″ ″ ″ 1:00/1:02 101 ″ ″ 30 5 ″ 0.3 ″ 0:55/0:56 102 ″ ″ ″ ″ ″ 0.4 ″ 1:10/1:12 103 ″ ″ ″ ″ ″ 0.45 ″ 1:17/1:18 104 ″ ″ ″ ″ ″ ″ ″ 1:28/1:28 105 ″ ″ ″ ″ ″ 0.48 ″ 4:34/4:34 106 ″ ″ ″ ″ ″ 0.5 ″ 4:49/4:49 107 ″ ″ ″ ″ ″ ″ ″ 4:28/4:28 108 ″ ″ ″ ″ ″ ″ ″ 8:00+ 109 ″ ″ ″ 6 ″ ″ ″ 2:55/2:28 110 ″ ″ ″ 7 ″ ″ ″ 1:11/1:12 111 18.5 35 30 5 1 0.48 422 1:15/1:16 112 ″ ″ ″ ″ ″ 0.5 ″ 3:12/3:12 113 ″ ″ ″ ″ ″ 0.52 ″ 7:00/7:00

TABLE VII Ex. 100 Thickening No. Density Mesh W-10 BA-58 FLR-1 APO 100 Temp. Time 114 18.5 35 30 5 1 0.48 422 0:57/0:58 115 ″ ″ ″ ″ ″ 0.52 ″ 1:00/1:01 116 ″ ″ ″ ″ ″ 0.6 ″ 1:13/1:13 117 ″ ″ ″ ″ ″ 0.65 ″ 118 ″ ″ ″ ″ ″ 0.7 ″ 119 ″ ″ ″ ″ ″ 0.8 ″

TABLE VIII Silica 100 Thickening Ex. W-10 Flour mesh BA-58 BA-11 FLR-1 ASA-500 DCA-229L Temp. Time No. Density % % % % % % % gps ° F. 70/100 Bc 121 17.5  10 35 8 1 1 0.5 0.1 312 1:51/1:52 122 ″ 15 ″ ″ ″ ″ ″ 0.2 ″ 5:13/5:13 123 ″ 10 ″ 6 ″ ″ ″ ″ ″ 124 18   25 35 8 1 1 0.5 0.1 345 1:20/1:20 125 ″ ″ ″ ″ ″ ″ ″ 0.2 ″ 2:48/2:49 126 ″ ″ ″ ″ ″ ″ 0.3 0.2 ″ 4:37/4:39 ″ ″ ″ 7 ″ ″ ″ ″ ″ 127 ″ ″ ″ 7 ″ ″ 0.5 0.25 ″ 42:16/42:16 128 ″ ″ ″ ″ ″ ″ ″ 0.3 ″ 76:19/76:20 129 ″ ″ ″ ″ ″ ″ ″ 0.4 ″ 81:31/81:31 130 16.4  35 8   1.5 1 0.3 0.15 370 3:14/3:14 131 ″ ″ 7 ″ ″ ″ ″ ″ 132 ″ ″ 6 ″ ″ ″ ″ ″ ″ ″ 5 ″ ″ ″ ″ ″ 8:07/8:08 133 ″ ″ ″ ″ ″ ″ 0.175 ″ 7:12/7:13 134 ″ ″ ″ ″ ″ 0.2 ″ 10:35/10:36 135 ″ ″ ″ 1 ″ 0.5 0.25 ″ 16:49/16:49 136 16.48 35 1   0.05 300 2:17 137 ″ ″ 0.075 ″ 2:44 138 ″ ″ 0.1 ″ 16:46  139 16.2  35 1   0.1 400 8:16 140 16.48 ″ ″ ″ ″ 7:47 141 16.48 35 1   0.1 500 2:14 142 ″ ″ ″ 0.2 ″ 9:23 143 16.48 35 1   0.3 600 3:44 144 ″ ″ ″ 0.4 ″ 4:05 145 ″ ″ 0.6 ″ 4:16 146 ″ ″ 0.8 ″ 4:09 147 ″ ″ 2 ″ 1:37

The Examples illustrate the ability of the cement slurries, when used in accordance with the invention, to thicken and exhibit high compressive strengths over extended periods of time. The presence of the copolymers in the cement slurries function to retard the setting of the cement, especially at elevated temperatures, as evidenced by the increased thickening times. The slurries do not require the presence of an intensifier. Further, the amount of copolymer required to demonstrate the desired degree of retardation is low.

From the foregoing, it will be observed that numerous variations and modifications may be effected without departing from the true spirit and scope of the novel concepts of the invention. 

1. A method of retarding the set time of a cementitious slurry introduced into a subterranean formation penetrated by a gas, oil or geothermal wellbore, comprising: introducing into the wellbore a cementitious slurry comprising water, a cement and a water-soluble or water-dispersible set retarder, the set retarder comprising a copolymer of repeating units of

wherein unit E represents a polymerizable ethylenically unsaturated monomer, the second monomer represents an alkoxylated sulfate, phosphate or ketonic salt and G represents an alkoxylated monomer of the formula:

wherein: R1 and R4 are independently selected from —H and a straight or branched chain C₁-C₄ alkyl; G is —CH₂— or —CH(CH₃)—; R2 and R5 are independently selected from a hydroxy substituted alkyl or alkylene having from 1 to 6 carbon atoms, —(CH₂CH₂—O—)_(n), —(CH₂CH(CH₃)—O—)_(n), —(CH(CH₃)CH₂—O—)_(n) or a mixture thereof; R6 is —CH₂— or —C═O; R7 is —H or a C₁-C₁₈ straight or branched alkyl chain or an acetate; X is an anionic radical selected from the group consisting of —SO₃ ⁻, —PO₃ ²⁻ or —COO⁻; Z is —H or a water soluble cationic moiety which counterbalances the valence of the anionic radical —X; n is from about 1 to about 150; c is a positive integer; and d and e are 0 or positive integers provided that d and e are not both 0; and allowing the slurry to harden to a solid mass.
 2. The method of claim 1, wherein d is
 0. 3. The method of claim 2, wherein E is a C₁-C₆ alkyl ester of a carboxylic acid, C₁-C₆ alkyl ester of an amido carboxylic acid, a hydroxylated C₁-C₆ alkyl ester of a carboxylic acid or a C₁-C₆ hydroxylated amido carboxylic acid ester.
 4. The method of claim 2, wherein E is selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methyl acrylamide, N,N-dimethyl acrylamide, N-isopropylacrylamide, maleic acid or anhydride, fumaric acid, itaconic acid, styrene, sulfonic acid, vinyl sulfonic acid, isopropenyl phosphonic acid, vinyl phosphonic acid, vinylidene di-phosphonic acid, 2-acrylamido-2-methylpropane sulfonic acid and mixtures thereof.
 5. The method of claim 4, wherein E is selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, maleic acid, maleic anhydride, fumaric acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid and water-soluble salts thereof.
 6. The method of claim 5, wherein E is acrylic acid or methacrylic acid.
 7. The method of claim 2, wherein the copolymer is of the formula:

wherein R4 is —H or lower C₁-C₄ alkyl, R5 is —(CH₂—CH₂—O—)_(n) or —(CH₂CH(CH₃)—O—)_(n) or —(CH(CH₃)CH₂—O—)_(n) or a mixture thereof, n is an integer of from 1 to about 40, R7 is —H, a C₁-C₄ alkyl or an acetate, R9 and R11 are independently selected from —H and —COOM, R10 is H or C₁-C₄ alkyl, and M is —H or a water soluble cation, c is the molar percentage being between from about 1 to about 99 molar %, e is the molar percentage being between from about 99 to about 1 molar %, and the total of c and e is 100%.
 8. The method of claim 7, wherein both R10 and R11 are —H.
 9. The method of claim 7, wherein R9 is —H and R10 is —CH₃.
 10. The method of claim 7, wherein R9 is —COOH and R10 is —H.
 11. The method of claim 2, wherein monomer G is selected from the group consisting of polyethylene glycol allyl ether (PEGAE), polypropylene glycol allyl ether, polyethylene glycol/propylene glycol allyl ether, hydroxyethyleneglycolmethyl methacrylate and methoxyethyleneglycolmethyl methacrylate.
 12. The method of claim 11, wherein the R7 group of the alkoxylated monomer is sulfonated.
 13. The method of claim 7, wherein R11 is —COOM.
 14. The method of claim 2, wherein the weight average molecular weight of the copolymer is between from about 1,000 to about 1,000,000 Daltons.
 15. A method of retarding the set time of a cementitious slurry until placed in a desired location within a gas, oil or geothermal wellbore, comprising: introducing into the wellbore a pumpable cementitious slurry comprising water, a cement and a water-soluble or water-dispersible set retarder, the set retarder comprising the copolymer represented by:

wherein: each R4 is independently selected from —H or a C₁-C₄ alkyl; each R5 is —(CH₂—CH₂—O)_(n) or —(CH₂CH(CH₃)O) or a mixture thereof; n is an integer of from 1 to about 40, each R7 is —H, —C₁-C₄ alkyl or an acetate; each R9 and R11 is independently selected from —H or —COOM; each R10 is H or C₁-C₄ alkyl; M is —H or a water soluble cation, c is the molar percentage being between from about 1 to about 99 molar %, e is the molar percentage being between from about 99 to about 1 molar %, and the total of c and e is 100%; and allowing the slurry to harden to a solid mass; the copolymer being present in the cementitious slurry in an amount sufficient to retard the set time of the cementitious slurry until the cementitious slurry is placed in the desired location within the wellbore.
 16. The method of claim 15, wherein the consistency of the cementitious slurry is between from about 1 to about 30 Bearden units of consistency.
 17. The method of claim 15, wherein the amount of water in the cementitious slurry is between from about 30 to about 150 weight percent based on the dry weight of the cement.
 18. The method of claim 15, wherein hardening of the cementitious slurry is delayed until the downhole temperature is greater than or equal to 500° F.
 19. The method of claim 15, wherein the cementitious slurry further contains at least one additive selected from the group consisting of fluid loss control additives, strength retrogression additives, permeability reducers, weighting materials, permeability reducers and anti-settling agents.
 20. The method of claim 15, wherein the alkoxylated monomer is selected from the group consisting of polyethylene glycol allyl ether (PEGAE), polypropylene glycol allyl ether, polyethylene glycol/propylene glycol allyl ether, hydroxyethyleneglycolmethyl methacrylate and methoxyethyleneglycolmethyl methacrylate. 